M. ML. Me TABLE OF CONTENTS INTRODUCTION CORROSION PRINCIPLES A. Why Metals Corrode B. The Corrosion Process C. Galvanic Corrosion of Tron and Stee? D._ The Corrosion Process as Related to Product ton and Gas METHODS OF CONTROLLING CORROSION A. Selection of Materials B. Protective Coatings £. Corrosion Inhibitors D. Cathodic Protect ion CORROSION IN GAS PLANTS CORROSION CONTROL OF OFFSHORE PRODUCTION EQUIPMENT A, Atmospheric Zone B. Tidal Zone C. Submerged Zone. 5. Equipment on Platform MONITORING AND SURVETLLANCE A, Inspection B. Corrasion Tests €! Chenical Tests APPENDIX A - CERTAIN REGULATIONS OF OFFICE OF PIPELINE SAFETY OPERATIONS PERTAINING TO CORROSION CONTROL 2 2 B B 32 58CORROSION - CAUSES AND CONTROL 1. INTRODUCTION AND SIGNIFICANCE The purposes of this lecture is to review the basic concepts of corrosion processes and corrosion prevent ion practices wich are relevant to produc ‘and gas engineering. These lecture notes form a supplenent to more detai Bresentations of this subject, a number of which are Tisted in Section VI age 37. The subject of corrosion is not as glamorous as many of the others presente during this school. Yet its economic significance is sufficient to justi high rating in almost any priority system which we could devise. The pers nature of the corrosion process contributes to the steady deterioration of of our metallic equipment, destroying not only its usefulness but our abil to carry on work in a safe responsible manner. Corrosion contributes both direct and indirect losses to the economic baiance sheet of our operat fons Some of these are: Direct Losses: 1. The cost of replacing and maintaining corroded equipment. 2. The cost of material and labor to provide corrosion prevention me: 3, The cost of corrosion al wance in the over-design of equipment. 4, The loss of of! and natural gas through corroded pipe. 5. Production losses during downtime for repairs. Indirect Losses: 1. The cost of bodily harm or add loss. ional safety precautions to avoid 2. The cost of environmental or ecological damage and the acconpanyir regulatory impact. 3. The cost of maintaining excessive inventories of replacement equi; These losses are exem have experienced. if ied in the following views of corrosion failures ¥ igure 1 shows a stub end of a ruptured 18-inch 1200 ps from corrosion, This abrupt and unexpected. fa Figure 2 si ine, causing 10: jon failure in a well f“Buy x08] asymayso yep 23949U09 UaY SuO}Sn|>U09 punos BujyrRes UL NO ys4sse 0} suo! aéunsse aqeuoseas pue {euoiz24 asn uayr ue> nok *ssa20ud uoLsouso> ayi 0 a{qissod Syoadse Aue se pubasiapun nof 41 ‘uanamoy “suoysn{au02 qwabi i {squL Yoead BLQP [LEAR e4EP 91434] 007 wes PULL [LLM NOX pue uaiqoud xo{dwod e SL siya ‘Aue "any, puadxe nu do Ue 10} uo} 4291040 uo} soJi0> 30 UNowe unwy xew pLAcid yeu; AEM e UL WeISKS Yor “a)uN yoka UB|Sep 04 sudsujBuS se AI) 401 ano $1 4] "paussou02 3q 09 uoseas yonu sy a4ay2 souey (duos £u0ze|M 2 uya2uo9 [equaWUOsj Aue *AqaJES *S>{WOUDI® Jo JuLodpUEyS PEO. B47 WO1s “OS “A Lugmuue uoy 2 $3509 uojsousoD uo. zouns bu deadde mou $3509 yons Avasnp 2 seaA Jad uo LLEq O26 02 wor oud yo 4800 aut. snid 1u Q2g paaxe 02 pare! poud S,uoxx3 "| enuue UOL LL 1W QOgs paaaxa Sujsnpoad S26 pue (10 ayy ul “Auasnpue (Le 8§ wouy aBued 03 poze rsa st uoL329;01d Wo} sou09 40 398448 9juoUOIe | [e12A0 Bul 382 Ayqouoseas auassip 326 ‘A que21JLUB]S suo, yeuedo S,uoxKa payoasse yore ‘saunlies 98449 Bsauj “yp [eyes @ UL paainsax yey2 au{J yse[L e pasned uOLsoluod jeusarUuL weal auaIM au} Si2NpOsd gd7 Youle & 4o Pode aun|yes aus sMous E aunbLyFIGURE 1 RUPTURED END OF 18-INCH 1200-PSI GAS GATHERING LINE FROM INTERNAL CORRO,“ALIWAVa ONY 3HI4 ONISNYD 3NIT d1 HONI -£ JO VAYV 3HNTIVS NOISONHOD & SuNDIS1. _CORROSTON PRINCIPLES Corrosion is defined as “the deterioration of a substance (usually a meta its properties because of a reaction with its environment". Our discussion involve only metals even though other materials also "corrode". We wi Timit our discussions to metals in contact with a liquid water environment, nature of which, a5 we shall see, is important in the corrosion reaction. Why Metals Corrode It can be shown by chemical thermodynamics that the driving force for any chemical reaction {s the chemical free energy; for any spontaneously occurr reaction the free energy change (denoted as 6) is negative. Stated anothe way, if we can calculate the free change for any chemical reaction and inc that it (16) is negative, we can say that there is a driving force to make Feaction go. On the other hand, if the calculation shows 6 to be positive ‘the reaction cannot take place without an external source of energy. For example, consider the reaction between 2 metal and oxygen to form a met oxide. If we calculate the free energy change for a nunber of metals, we arrive at the values shown in Table 1. TABLE 1 Free energies of some metal oxides (In Cal/Mole) A203 -376,700 Me 0 -126,130 0 ~ 76,080 Fep03 -177,100 Fe30q 242,000 cud ~ 30,400 90 + 2,600 A203 + 18,810 Note that aluminum ox a strong tendency for s oxide ( je has a very large negative 6, indicating that the to form spontaneously. Conversely, it is difficu without application of high temper }, does not form spon Copper oxide has a small negative G, and as on expect, is more easily reduced than What these nunbers me essence 1s that from free energy standpoint, aluminum will tend to form-4930M w3s: }quaaed aay azadsau apays uo paseg s1 uOLUM aLqea ae Lyuys e uj pebuEJse (@ pue Seyou voMNOD aioym ‘12>132e1d Suou Yon St ‘SaLJas 2[UeALeD ayy qe "woy30q ayy 4e SLeyeM (a[qoL) aA; y2ee4-voU 243 pue 9[qeL By2 40 dor 2 S(pqau (2sPq) 34,32" B42 UTIM “pOqeD1 pu sy Leyau aus 40 Asal aDe—04 ‘yz ‘sanaMoy “A LaALIEIL LEN “UOL eyau 344 Jo Uo} yeAqUBDUOD (4394 [/a Lou T uxosdde) paxys @ ururequ0d suoinjos 03 A [uo Ade ,3 Jo sanjer 243 dou) a Buyaseuybus 91394 | sey z 91gei yeu; suedw ose stuf “u0149e=4 Uo1 s0J40> ‘943 uO sMy2 puk [2}3usI0d 9pO4729[2 a42 UO 422449 punosoud e sey UOLINLOS Uj Suoy Jo Uojzesqusouod ayy yey azi [ved 0} UeJodM S| I] “saseadz—p luo}32ea4 a3 405 29405 BULALAD 843 “S4oJas0y] pue “saseousep [eLquez0d aur uy oF ynLoOs 347 UL suo! 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[exau 242 40 Aouapuey ue [ejay yeunyanas 1a p08 “sh Usea Kuan aplxoTABLE 2 Electronotive Force Series wr ne =H Standard Electrode Reduct fon Potential, E* (volts) 2. Potassium tanganes Zine (an) in (Sn i Copper ut Mercury (Hg' Platinum, (P Reference Electrodes: SCE + 0.24 Ag/Agcl + 0.26 Cu/CuS0g + 0.32(queqsy se4-uoysoiu0s you 10 21 poyzea) pug p23983044 unuy ae Ld (enjssed) ss0quyeas ote ad (an $508) ssouters Hoe aah, A138ed) Ubas yuo. 99H) L292EN peor s4@plo§ us3-pea7 sa luIeIS OTE edAL (2n1y3e) $53 ULBaS poe aah) uouT 3S) 25|S3y-1N (@nry9e) wody-unwo.a4yg oar 38e9 oul 40 1289s (sz) oort wnt a sol ty unysuBey pue unt saubeyi (ques sas-uoysoiso> yseaj Jo ‘otpoue) pug papo.i0g 922me9S BuLMOLY UL SKoLiy pue SLP32W 40 S3j4a5 2\UeRie9 © may.Tt should be noted that there is no way to measure the potential of a sing etal electrode without making a second contact with the solution. In ord measure the potentials listed in the EMF Series, an arbitraty reference el the hydrogen electrode, is designated as having zero potential and al1 oth potentials are referred to it. Since the hydragen electrade fs inconveni for practical use, other reference electrodes are preferred. The thre connon are the saturated calonel electrode, the silver/silver chloride and the copper/saturated copper sulfate electrode. Galvanic Cells, Electrolytes, Anodes and Cathodes Knowing how individual met in solu we next consider the galvan' far metal Such as copper and zine are inmerséd in a solution. Consider the copper-z arrangement shown in Figure 4. From our Table of electrode potentials, we that a copper electrode has a potential of about 40.35 volts, and the zinc electrode a potential of -0.76 volts. Therefore, if we were to short the terminals of the two electrodes, we would expect an initial driving voltag about 1:10 volts, Current will flow through the external metal circuit fr copper to zinc, then through the solution from zinc to copper. The resist of an electrolyte (a solution containing ions) depends on the anount of di present, but is generally at least a million times greater than the vity of the metallic paths, and therefore the resistance of the sol usual ly governs the current flow. In Figure 4, current Flows (remember that conventional current flow is pos inich is opposite to electron flow) in the external circuit the copper electrode to the zinc electrode; the zine starts to dissolve, ¢ into solution as zinc fons: In—rIn ++ +26 charged ions migrate toward the copper electrodes and if copper ly present in solution, they will plate out: cut + 2e ecu As a result, the zinc electrode is slowly dissolved or corroded while the copper electrode remains the same (or actually grows, if enough copper is present in solution). The electrode at which the metal goes into solution (i.e. solut current enters in) 1s called the ANODE and is ox{dized or corroded: The electrode which current Teaves the solution and enters the metal is called the CATHC reduced. Normally, no corrosion occurs at the cathode.USVI NOMIVZIEWIOd 9 Old anauuno ‘sony T ' { i ' 4 aywes > ZO. ww003 HED ONIZ-WSadOS "old ‘awunaios NolLAI0s S4¥aTHS Waddoo 9 3ivsIns ON anzano waeeoo one non Mong ana nowslS33Polarization The electrode potentials referred to so far have been equil ibrium or open-: » the potential with no current flowing. hhenever current ‘an electrode, the potential of that electrode will change an anount depending on the direction and quantity of current. The extent « the potential change, measured in volts, is called POLARIZATION. The dire: ‘of the potential change is always such as to oppose the current flow. Flows to or As an example of polarization, consider once more the coppe Figure 4. If there is no external current path ‘open electrodes each have a characteristic potential as given pr 5, these potentials are plotted at zero current on a potent: urrent gra When a small anount of current is allowed to flow through the external cir: the potential of the electrodes changes slightly; the copper electrode bec more anodic, and the zinc electrode more cathodic. As more and more curre allowed to flow, the potent ials continue to change (POLARIZE) and the pote difference between the two electrodes decreases to a value limited by the resist ivity of the electrolyte sol ‘The ameter will show 2 current flow of Icopr which is quant. related to the rate at which the zine electrode is dissol Po! n thus has the effect of red ‘the current flow (corrosion of a corrosion circuit as time passes. phenomenon is a quite common-place occurrence. Some common causes of polarization are; a buildup of corrosion product fi the am uildup of a gas bubble layer; presence of corrosion inhibitors especially chronates; passage of impressed direct current (cathodic and an protect io Some of the causes of decreased polarization ( resistivity electrolytes; stirring, presence dissolved oxygen, or sulfate reducing bacteri \ereased corrosion) are: 1 depolarizing agents such a increased temperature. C. Galvanic Corrosion of Iron and Steel Iron, with an electrode potential of -0.44 volts, occupies a position near middle of Table ced the zinc electrode in Figure 4 with an 4 he driving potential of the galvanic cell would be less but co nd iron would be the anode and would slowly }f the copper electrode were replaced with th “zine galvanic couple, the iron would become ‘the zinc continued to be the anode. It is corrode. iron electrode, giving an cathode and not corrode, that whenever iron is coupled with a metal below it in the table, thi becomes the anode and corrodes, whereas if iron is coupled with a metal ab it in the Table, the iron becomes the cathode and do: has great practical significance: we must avoid cou not corrode. This ing steel metals, and we can use metals such as zinc and magnesium to pro\ for our steel structures. The insertion of a bronze check valv 1 1e (Figure 6) is an example of galvanic coupling. This is pat rious if the area of the anodic metal in the couple is sign than the cathode, The concentrat ion of corrasion on the small anode area+2404 uoysousos ySty @ ub aunsa4 ‘pides £u9n aq ue> uo}z2%24 siuy ‘arxjos39919 ayy 40 4149198 249. 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The cost of this fiber in the lover pressure range is comparable to the cost of steel pipe. The glass epoxy pipe is available as tubing and 1s being used for injection tu in salt water disposal particularly where backwashing by gas or air practiced, and where water wells are produced by airlift. A number of lin tations still exist affecting the use of fiber glass epoxy pipe, including Ine of glued-type connectors, susceptibility to sand cutting, external collapse and abrasion, and excessive thermal expan: You should be ver efore, in use of fiber glass epoxy pipe in order not to exce 1s. in the application you have in mind. Brands of fiberglass Texas Fiberglass Products. Cenent asbestos pipe is widely used for salt water gathering lines and as source water lines for waterfloods. It is inert to most corrosive fluids handled in the oil field and the internally epoxy-coated cement asbestos p has advantageous use where paraffin and corrosion in flow! ines are a pro Special precautions are required in laying this pipe and it is not entirel adaptable for use in rough terrain. B, Protective Coatings Protective coatings are a widely used method of mitigation of corrosion of surface equipment, tubular goods, and underground pipelines. The maintena of an inert impermeable barrier Between the metal to be protected and the corrosive environment will effectively prevent corrosfon act ion on metal. Metallic Coatings. Many processes are used for applying metallic type coa Fncluding hot étpping, cenentation, mechanical cladding, electroplating, spraying, ard condensation of metal vapor. Hot dipping is @ widely used process for corrosion protection of steel by galvanizing and tinning. Galvanized sheet is widely used in the petrol eur Yndustry in the fabrication of of1 storage tanks. Cladding involves veneering of the base metal plate with a more noble mete under pressure, Such cladding of equipment is widely used in the petroche industry. Electropl, sa most important method for production of protective net coat ings. process deposits coatings that are more uniform than hot-d coatings and Tess porous than sprayed coatings. Electroplated chromium widely used in the production of liners and pistons for reciprocating pump Viners in barrels for subsurface punps. Inorganic Coatings. Inorganic coatings consist of four eal or electrachemical surface corrosion coat ings, ) cementation coatings, and (4) zinc rich coatings. eral. groups: vitreous enane The chenical or electrochentcal_ surface corrosion coarings often only serv489 wai -auole uorsynl@ quabiqWoopiy aud us asm UL Sue sauyi az15 Yul oT Ni-2 403984 000°000"E s2AO pue “BuLuLL siya ya4m paujeyqo UBaq sey aD,\—a5 9x9 “S9U}| UOL}D—FUy saqOM uy ALaAjSuaIX® pas O5|2 st adyd paul [-qUEUE] + saueyzauné lod \Muzatjod ‘suaysak tod ouaud aingeueduey y8)y pue Axoda-apizeuphy se yons sadé ‘sayxoda se [209 se yans ‘aphuapleuos louayd pe 'u) 40p pasn $6uj3209 213se[d "SLaSSeA snolen pue *SauL| Moly “Buygny uj uoysoau09 Buj|10J3ud9 Jo sueeu eAxsz2a449 UE uDEq aney pasn pur pal Ldde ‘DaLSn{2¥9 9q 02 P9pustu} 30U S1 3841 ay2 pue padolsnep Gujaq sAemye ae saay3) “f4asMpuy 242 UL pasn S6uL2e0D ST 5954 ,S6US3209 [euuaquy $0 $9)45)1939e4049, y algeL “adud aul |_pue Gurgns 40 Buiz202 YeUsaqU] 40} BLqeL}eAe ase SBuyjeoo Jo sadky Auey “SbULFeOD edjg [eUseIU +26ne6 wits Aap 4saq04%1H 40 say2W02|3 ue Aq paunseaw aq pno¥s Kap pur of A0sey pur Jayut] © asn y A04 *SSEUADLUR ULES pue sKEpL toy 40s Gu 3DadsuL U}340M 5p of Guy3209 Ue pue 10}9>4 \dde au Ue? 494I9q S| GuI7209 ON “Ss eyaayew Suy3209 40 uoLy29495, ) pue aunsodxa 30 suoy31 puoo yequewuosyaus ays (€) “uoLqeiedaid aoesans (2) [eyau seq Jo aanyeu (T) ase asey) “uo}qUEzIe [NJa4e> aALe2a4 ysnu $407 )q uje3sa9 Buy 3209 Aue Jo aoueusosaad £40392454 72S 40} FeYy [eLqUISSE St IT 1B uo} 32a1as apyaoud 03 uo pal Lex aq pinous vou6 Guy s99u)6u3 1,449 Uo sanof $3829 [[e Wj pue ‘pa4apjsuo> aq pinous S3anpoud anigizaduod £40292sS| eS "su [qosd L4aAL (ap pue A[ddns quanbady ‘ney OYA *330932H 02 pOISOALD SEM SSEU\SNq SLY." 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In genera’ coated external ty Unfess a) fhe expected serv can be substantiated that external corrosion will not be a problem, New 0 replaced lines subject to Deptartment af Transportation regulation are req to be externally coated. Exxon specifications concerning external coatings should be observed in al cases. Approved coating systems include either the A-1 or A-2 systems or tape system such as Plicofiex #340-25. The A-l and A-2 systens involve us asphalt or coal tar enamels with felt wrapper (A-2 includes glass fiber re forcement) and kraft paper outer wrap. Your Division Engineering gr should be consulted concerning application of these specifications. C. Corrosion Inhibitors amounts in a corr There are two composition: iy material used in very s ly reduce the rate of corro: ‘inhibitors based on chemi A corrosion inhibitor 4: environment to substant general types of corros: Inorganic corrosion inhibitors, including chromates, phosphates, nitr and arsenic compounds . Organic corrosion inhibitors, which are polar molecules usually conta nitrogen. Examples are anine salts, amides, and quaternary anmoniun chlorides. A corrosion inhibitor works by attaching itself to the anodic and cathodic areas of the metal surface and interfering with the corrosion reaction, Fi 18. “Sone inhibitors absorb only on the cathodic area or only on the anod area. These inhibitors are termed cathodic or anodic inhibitors. Anodic inhibitors are referred to as “dangerous” inhibitors because when used in insufficient concentration, they cause pitting by exposing limited portion area to severely concentrated attack. Sodium chromate is a inhibitor. Although it is extremely effective in reducing fresh water systems, it promotes pitting in an environment containing sod chloride, because the chloride ion breaks down the anadic Film, Organic inhibitors, generally classified as cathodic inhibitors, are used extensively in oi1’and gas production streams for internally protecting tul ities, and portions of the process are: flow! ines, salt water hand] ing fac proprietary formula’ gas handling facilities. These inarketed by conpanies sich as Ex Nalco (Visco) to sone exter others are ofl-soluble, and st phase. These inh fog ard gS type to'suifigé stress crack ing, but proper chotce of metal uray rather ition should be depended upon for this resistance, They are not. part effective against oxygen-related corrosion. @ number of such’ inhibitors, each de: ations. Sone inhibitors are water solub other are dispersible in one or the othe) better than 95 percent protect ir jtting corrosion. 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